1227384 玖、發明說明： 【發明所屬之技術領域】 本發明涉及一種用於電子照相的調色黏合劑，用來以 電子照相、靜電記錄、靜電印刷及諸如此類方式顯影靜電 荷圖像’具體地說’本發明涉及一種用於電子照相的調色 劑，其用於高速影印機中，解析度高、圖像質量好，還具 有優異的可磨性。 【先前技術】 目别在PPC影印機或印刷機中通常使用電子照相 法，其中調色圖像形成於光電導體上，然後轉錄到記錄紙 上（Plain Paper Copy Method )，從而靜電潛像形成於光電 導體上，然後用調色劑顯影潛像，將調色圖像轉錄到被固 定的印刷品上如紙或類似的印刷品，用加熱輥加熱，以便 定影轉錄圖像。因爲在加熱及加壓下定影，所以這種方法 可以快速進行，並且熱效率非常高，因而定影效率也很 =。雖然加熱輥法具有良好的熱效率，但當調色劑爲溶融 態時’調色劑與加熱輥的表面接觸，在黏合作用下，調色 劑轉移到加熱輥的表面上，轉移的調色劑再轉移到固定的 下-印刷品上，從而弄髒了印刷品（偏移現象）。 機器安裝、 法不可取。 用布或紙將石夕油塗敷在加熱輥的表面上，可以防止偏 移現象發生。雖然這種方法防止調色劑的偏移效果很好， 但需要-種設備’以供應防止偏移現象發生的液體，而且 維修和官理複雜，所以成本較高，因兩 而且由於加熱，矽油等物質容易揮發， 因而這種方 發，從而弄 1227384 髒機器的内部。 口而i希望開發研究—種用於高速機（無油定， 法）的調色劑，在該方法中，不需要塗敷上述的石夕油等: 質（無油定影法）。 一另外，當影印機指向高速時，定影輥的速度必然报 南，调色劑必需在短時間内通過加熱定影。爲了在短時間 内疋& ’调色劑在溶融態時，流動性必需很高。雖然降低 用作調色劑的樹脂的玻璃化轉變溫度（下面稱_ U)可 以有效地改善定影性能，但在貯存過程中，常出現所不希 望的現象如調色劑結塊。 …另外’已有許多方法使用交聯聚合物防止調色劑在無 油疋影法中偏移。如日本專利特許公開號6()_36582中公 開了一種使用由乳液聚合法製備的交聯聚合物的方法，在 該方法中，所用的交聯聚合物含5㈣質量％凝膠，當凝 膠的a里增加日守’改善抗偏移性，但可磨性變差，而合 膠的含量降低時，改善了可磨性，但抗偏移性下降。戶;以 很難同時改善抗偏移性和可磨性。 “方法中，备製備交聯聚合物時，必須同時使 用分散劑或分散助劑，以便使乳化粒子穩定。但這些分散 =是高吸，性，，嚴重影響其電性能，尤其是電荷穩定 j以製備乂聯聚合物後，必須盡可能地除去這些分散 k樣就而要大置的勞動力’而且排水量和處理量也很 另外USP4,966,829中公開了一種方法，其中使用含 乙稀基聚合物的調色劑效果較好，所述乙稀基聚合物含 1227384 0·1.質量％凝膠，在四氫吱喃的可溶部分中，主峰的分 子量爲MOO-25,000，還有至少—個分子量範圍爲 3广0-150,000的亞峰或尖峰。但因製備這種聚合物的方法 爲4浮液聚合法’與乳液聚合法相似，必須同時使用分散 劍或分散助劑’所以還是具有與上述乳液聚合法相同的問 題。爲解決上述問題，本發明人開發了一種通過溶液聚合 法製備的樹脂’該樹脂可以用作具有良好定影性的調色劑 (USP 號 4,963,456)。 在由溶液聚合法製備的樹脂中，當聚合完成後，除去籲 岭d。此時可以除去所有的低沸點組份包括未反應的殘留 單體和引發劑的分解産物，其中用作調色劑的最佳樹脂， 爲含少量的不純物和電性能穩定的均相樹脂。但用溶液聚 合法製備交聯聚合物時’由於魏森貝格效應（樹脂纏繞在 攪拌棒上）的影響，很難製備交聯聚合物。因此本發明人 還研究開發了 一種用本體聚合等方法製備分子量盡可能 高的聚合物的方法（USP號5,〇84,368)。但製備的聚合物 的分子量有限，所以沒有完全克服偏移性的缺點。 _ 另外’日本專利公報號6〇-38700中公開了一種用加 熱和混合含縮水甘油基的3-4〇%單體的共聚物（A)和交 聯化合物（B )製備的調色黏合劑，效果較好，但這種調 _ 色劑的舞命有限，在長期試驗中，因爲有許多環氧基殘 基，所以出現了帶相反電荷的調色劑。 而且本發明人還研究了一種通過比率一定的樹脂和 化合物的交聯，以製備性能優異的調色劑的方法，其中所 7 1227384 述樹脂含有通過溶液聚合法製備的幾基，而所述化合物含 有縮水甘油基（曰本專利特許公開〇6 〇ιΐ89〇和 22612 )通過違方法製備的調色劑可以用於高速機 中’其定影性、偏移性和結塊性之間具有良好的平衡性， 而且可磨性、電性能和電荷穩定性好、生纽率高。但在 製備調色劑的捏合過程中，當交聯組份受到過度的剪切作 用切割凝膠時’在高溫時，調色劑的彈性不夠從而定影 後，圖像的質量變差，而且*能獲得足夠的偏移效果。 本發明人認真地研究了爲#足上述要求的必要條 件^從而開發了 -種通過提高含縮水甘油基的交聯劑的分 子里和％氧值，以製備性能優異的調色黏合劑的方法（日 本專利特許公開號〇9_31914〇)。所製備的調色黏合劑可以 降低在製備調色劑的捏合過程中凝膠的切割影響，而且具 有良好的持續顯影性和抗偏移性，同時極大地改善了定影 性、抗偏移性和結塊性之間的平衡性、還具有優異的可^ 性、生産效率、電性能和電荷穩定性。 但是’目丽市場需要高速節能的新技術。因而需要通 過高速技術減少加熱時間，從而降低定影溫度，通過節能 降低定影溫度。但進一步降低溫度時，滿足定影性的條件 很苛刻’所以通過上述方法’很難同時滿足進一步降低溫 度時的定影性和抗偏移性所需的條件。 【發明内容】 爲了滿足影印機市場的高速和節能的需要，同時改善 低溫時的定影性及定影性和抗偏移性之間的平衡，本發明 1227384 的一個目的是改善用於電子照相的調色劑的所有性能，包 括定影性、抗偏移性、結塊性、可磨性和持續顯影性。 本發明人認真研究滿足上述需求的這些必要條件，結 果發現，在通過交聯化合物和共聚物的交聯製備用於電子 照相的調色黏合劑時，在反應過程中，停止交聯反應，以 製備低黏度的調色黏合劑，從而改善定影性，在定影過程 中，利用存留的交聯活性繼續進行交聯反應，從而改善偏 移性、同時改善可磨性、結塊性和持續顯影性。已經完成 種製備用於電子照相的調色黏合劑的技術，其用於高速 _ 印刷機中，具有優異的定影性、抗偏移性、結塊性、抗磨 性和持續顯影性，在140-180°C的範圍内，黏-彈曲線爲凹 形’其中曲線的底端表示最小值〇□〇，同時還具體地表示 了上述最小值GOO和200°C時的貯存模量G[]2〇〇之間的 差。 _ 下面具體描述本發明。 (1) 一種用於電子照相的調色黏合劑，其中在5〇_2〇〇 C範圍内，加熱速率爲2°c /min的條件下，測量調色黏合 _ 劑的黏-彈性，於100-200X：範圍内的黏_彈曲線表明了貯 存模量和溫度之間的關係，其中曲線的縱坐標爲貯存模量 G的對數（pa)，橫坐標爲溫度（它），在14〇_18〇。〇範圍 · 時，曲線爲凹形，曲線的底端表示貯存模量G，的最小值 夢 G O’G’O和200°C時的貯存模量G，200之間的關係爲G，〇< G，200,其差值△ G，（ G，200_ G，〇=A g，）爲 3〇〇Pa 或 3〇〇 pa 以上。 9 1227384 (2 )根據（1 )中所述的用於電子照相的調色黏合劑， 其中上述的貯存模量在200°c時的值爲1000 Pa或1000 Pa 以上。 (3 )根據（1 )或（2 )中所述的用於電子照相的調 色黏合劑，其中該調色黏合劑的玻璃化轉變溫度爲45-75 °C，含0.1-20質量％凝膠，在4,〇〇〇__5〇,〇00分子量範圍内 有一峰值’根據四氫呋喃中的調色黏合劑的可溶部分的凝 膠滲透色譜法測定的分子量分佈。 (4 )根據（1 ) - ( 3 )中任何一項所述的用於電子照 相的調色黏合劑，其中交聯反應度爲U0%。 (5 )根據（1 ) - ( 4 )中任何一項所述的用於電子照 相的調色黏合劑，其中調色黏合劑是通過加熱和熔融含縮 水甘油基的乙烯基樹脂（A)和含羧基的乙烯基樹脂（b) 製備的，所述乙烯基樹脂（A)的重均分子量爲 10,000-100,000，環氧值爲 〇 〇〇5-〇 1Eq/1〇〇g，樹脂（B) 的酸值爲l-30mgKOH/g，玻璃化轉變溫度爲4〇_7〇〇c，爲 了交聯，使用上述的含縮水甘油基的乙烯樹脂（A)作爲 交聯劑。 (6 )根據（1 ) _ ( 5 )中任何一項所述的用於電子照 相的調色黏合劑，其中苯乙烯_丙烯酸樹脂中的一種樹脂 作爲主組組分。 (7) —種用於電子照相的調色劑，其中使用上述（1) -(6)中任何一項所述的用於電子照相的調色黏合劑。 l227384 【實施方式】 〜本發明的含縮水甘油基的乙烯基樹脂（A)是通過含 縮尺甘油基的乙稀基單體和另外—種乙烯基單體共聚製 備的，作爲含縮水甘油基的乙稀基樹脂⑷，優選聚合物 的重均分子量在10，__1〇〇，_範圍内，更優選Μ，麵_ 85,〇〇〇,最優選25，__75，_，環氧值爲〇惠〇，iEq/ i〇〇g，根據JISK7236標準測定的。如果重均分子量小於 ιο’οοο,在製備電子照相的調色劑的捏合過程中凝膠容 易被剪切，而且在定影後，持續顯影性和抗偏移性下降；隹 如果重均分子量大於100,000，定影性變差。另外環氧值 優選在Ο·01·0.1 Eq/l〇〇g範圍内。如果環氧值小於〇〇〇5 Eq/l〇〇g，凝膠的生産量和抗偏移性下降；如果環氧值大 於ο·1 ’製備電子照相的調色劑捏合過程中，凝膠容易被 勇切’持續顯影性和抗偏移性下降。 本發明的含羧基的乙烯基樹脂（B)是通過含緩基的 乙烯基單體和其他乙烯基單體共聚製備的，含羧基的乙稀 基樹脂（B)的酸值優選爲，根據JISk54〇7 · 標準測定的。Tg爲40-70°C，根據JIS K7121標準測定的。 更優選酸值爲5-25 mg KOH/g、Tg爲50-6(TC。如果Tg 小於40°C，容易結塊；如果Tg大於70°C，軟化點升高， · 定影性變差。如果酸值小於1 mg KOH/g，每一分子的反 應量低’分子量很難變高；如果酸值大於30 mg KOH/g， 在製備電子照相的調色劑的捏合過程中，凝膠容易被剪 切，持續顯影性和抗偏移性降低。 11 1227384 本發明的用於電子照相的調色黏合劑是通過加熱和 炫融含縮水甘油基的乙烯基樹脂（A)和含被交聯的魏基 的乙烯基樹脂（B)製備的，調色黏合劑含G.l_20%凝膠， 優選1-2G%，更優選。如果用於電子照相的調色黏 合劑中的凝膠的百分比小於〇·1%，很難具有抗偏移性的 =果；如果凝膠組的百分比大於2〇%，流動性下降，低溫 蚪，定影性變差很難用於高速運轉的影印機中。 另外優選使用含縮水甘油基的乙烯基樹脂（Α)和含 羧基的乙烯基樹脂（Β)進行交聯反應，其中所述甘油基籲 的含Ϊ爲0.01-1 ·〇克當量、優選〇 〇2 〇 8克當量，每一克 當量的羧基相當於一縮水甘油基。 在本發明中製備含縮水甘油基的乙烯基樹脂（Α)時 使用的含縮水甘油基的乙烯基單體的例子有，如丙烯酸縮 水甘油酯、丙烯酸沒-甲基縮水甘油酯、曱基丙烯酸縮水 甘油酯、甲基丙烯酸石—甲基縮水甘油酯等，但優選甲基 丙烯酸縮水甘油酯、甲基丙稀酸甲基縮水甘油酯。這 些含縮水甘油基的乙烯基單體可以單獨使用或兩種或兩 籲 種以上結合使用。 在本發明中製備含羧基的乙烯基樹脂（Β)時使用的 含羧基（包括不飽和多元羧酸的酸酐）的乙烯基單體的例 子有，如不飽和二元酸的單酯，包括丙烯酸、甲基丙烯酸、 馬來酸酐、馬來酸、富馬酸、肉桂酸的單酯、富馬酸甲酯、 畐馬酉夂乙酯、畐馬酸丙酯、富馬酸丁酯、富馬酸辛酯、馬 來酸甲ί旨、馬來酸乙酯、馬來酸丙酯、馬來酸丁酯、和馬 12 1227384 來酸辛酯，優選丙烯酸、甲基丙烯酸、富馬酸的單酯、富 馬酸甲6旨、富馬酸乙δ旨、富馬酸丙g旨、富馬酸丁 g旨、富馬 酸辛酯。這些含羧基的乙烯基單體可以單獨使用或兩種或 兩種以上結合使用。 作爲與含縮水甘油基的乙烯基單體和含羧基的乙烯 基早體共聚的乙細基早體的例子有，苯乙稀類包括苯乙 烯、對-甲基苯乙烯、和α -甲基苯乙烯；丙烯酸酯類包括 丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、丙 浠酸辛酯、丙烯酸環己酯、丙烯酸硬脂酸酯、丙稀酸苄酯、 丙浠酸糠酯、丙烯酸羥乙酯、丙烯酸羥丁酯、丙烯酸二甲 基氣基甲S旨和丙稀酸一^甲基氨基乙S旨；甲基丙稀酸醋類包 括甲基丙烯酸甲酯、曱基丙烯酸乙酯、甲基丙烯酸丙酯、 甲基丙烯酸丁酯、甲基丙稀酸辛酯、甲基丙烯酸環己酯、 甲基丙烯酸硬脂酸酯、甲基丙烯酸苄酯、甲基丙烯酸糠 酯、甲基丙烯酸羥乙酯、甲基丙浠酸羥丁酯、甲基丙烯酸 二曱基氨基甲酯和甲基丙烯酸二甲基氨基乙酯；不飽和二 元酸的二酯類包括富馬酸二甲酯、富馬酸二丁酯、富馬酸 二辛酯、馬來酸二甲酯、馬來酸二丁酯、馬來酸二辛酯； 和醯胺類包括丙烯腈、甲基丙烯腈、丙烯醯胺、曱基丙烯 醯胺、Ν-取代的丙烯醯胺、和N-取代的甲基丙烯醯胺； 在這些乙烯基單體中，使用至少一種乙烯基單體。其中特 別優選的單體包括笨乙烯、丙烯酸酯、甲基丙烯酸酯、富 馬酸二烷基酯、丙烯腈、丙烯醯胺、曱基丙烯醯胺等。這 些乙烯基單體可以單獨使用或兩種或兩種以上結合使用。 13 1227384 數均刀子里和重均分子量爲根據GPC (gel permeation chromatography)法測定的對比分子量，用單分散的標準聚 苯乙烯緣製校準曲線。測試條件如下： GPC 設備；JASCO TWINCLE HPLC 檢測器；SHODEX RI SE-31 柱；SHODEX GPCA-80M* 2 + KF-802 溶劑；四氫吱喃 流率；1.2ml/min 本發明的凝膠份的百分比根據下面測試的值來確籲 定。將2.5g的樹脂和47.5g的乙酸乙酯放入1〇〇ml的樣品 試官中，在22°C下，以50轉/分的轉數攪拌12小時後， 樣品試管在22°Cf，靜止放置12小時。然後，將樣品試 管中的5g上清夜在15(rc下乾燥i小時，稱量産品的質量 (Xg)，根據下面的通式計算凝膠的百分比。 凝膠（％) ={ ( 2.5/50-X/5) /(2 5/5〇)}χ1〇〇 關於用本發明的聚合物（A)和（B)製備用於電子 照相的調色黏合劑，可以採用下面的方法及類似的方法，# 其中所述聚合物（B)爲含絲的乙烯基樹脂（B)，所述 聚合物（A)爲含縮水甘油基的乙烯基樹脂（a)。含縮水 甘油基的乙烯基樹脂（A)與含絲的乙稀基樹脂⑻ 在Hensehel混合㈣容器中混合，在雙軸捏合機中融化， 捏合’以錢基和縮水甘油基進行交聯反應。 · 在樹脂（A )和樹脂f d、 w月曰C B )的交聯反應中，停止交聯 反應，利用殘留的交聯法把制μ ' 聯，舌性製備用於電子照相的調色黏合 14 1227384 劑’根據該方法製備的調色黏合劑的黏度低，因而改善其 定影性。另外在交聯反應中，當交聯反應完成時（這以完 全反應的凝膠含量表示），凝膠的含量爲15〇%，優選 更優冑5_45% ’以便衫影時，借助留存的交聯 活性（這以交聯反應的程度表示，根據下面的通式確定交 聯反應度(凝膠（％)/完全反應的凝膠（％)χΐ〇〇) 繼續進行交聯反應。爲達此目的，優選雙軸捏合機的釋放 口的樹脂溫度爲165°c -19(rc以下時，停留時間爲9〇·ΐ8〇 秒時融化和捏合樹脂，當雙軸捏合機的釋放口的樹脂溫度籲 在190-200。〇範圍時，停留時間小於9〇秒。 另外，當樹脂在雙軸捏合機的排放口的樹脂溫度22〇 °C，捏合時間爲180秒内反應時的凝膠含量定義爲交聯反 應完成時的凝膠含量，即完全反應的凝膠含量。 將用該方法製備的樹脂冷卻並研磨，以製備用於電子 照相的調色黏合劑。雖然可以採用目前常用的冷卻和研磨 法’但優選用鋼帶等物質驟冷樹脂的冷卻法。 本發明中關於融熔和捏合樹脂（A)和樹脂（B)，以 _ 使它們進行交聯反應的方法，可以用目前常用的加熱和熔 融樹脂法，但優選使用雙轴捏合機的方法。 根據本發明製備的電子照相調色黏合劑，在5〇_2〇〇 · °C範圍内，升溫速率爲2°C/min的條件下，測試黏-彈性， · 100-200°C範圍内的黏-彈曲線表示貯存模量和溫度之間的 關係，曲線的縱坐標表示貯存模量G >的對數（Pa )，橫 坐標表示溫度（°C )，在140-180°C範圍内，黏_彈曲線爲 15 1227384 凹形，曲線的底端表示貯存模量的最小值G > 〇，溫度爲2〇〇 c時的貯存模量G/ 200優選爲1〇〇〇 5〇〇〇〇Pa，更優選 2000-40000Pa，最優選 3〇〇〇 2〇〇〇〇pa，G / 〇 和 2〇〇。〇時 的貯存模量200的關係爲（}/ 0< 200，其差值△ G ( G 200_ G / 〇=△ g -)優選爲 3〇〇 5〇〇〇〇pa，更優 選 400-40000 Pa，最優選 5〇〇 3〇〇〇〇 pa。 如果貯存模量G 200小於1〇〇〇 pa，高溫時，黏度降 低，很難侍到足夠的抗偏移性。而且如果△ G，<3〇〇 pa， 疋〜〖生和抗偏移性很難平衡，雖然低溫度時定影性好，但 定影性和抗偏便移性之間很難達到平衡。 另外，本發明的用於電子照相的調色黏合劑的丁名優 選爲45-751，更優選爲45_7〇。〇，最優選爲5〇_坑，上 f的用於電子照相的調色黏合劑中的四氫吱喃中的可溶 部分的分子量範圍優選爲4,〇〇〇 5〇,〇〇〇，更優選 〇 40,00G ’最優選8，咖_3G，刪根據凝膠渗透色譜法 (GPC)測定的分子量分佈。 八^ ^ ^小於45 C ’容易結塊’如果Tg大於75°C或 、子里的峰值超過5〇,〇〇〇 ’樹脂變硬，定影性變差。如果 为子量的峰值小於4,000,容易發生偏移現象。 通過已知的方法，使用本發明的用於電子照相的調色 展石劑與著色劑可以製備用於電子照相的調色劑，如有必 ，逛可以使用電荷控制劑、釋放劑、和顏料分散劑。 者色劑的例子有，如黑色顏料包括碳黑、乙快黑、燈 …和磁鐵礦；鉻黃；黃色氧化鐵；和常用的有機和無機 !227384 顏料包括Hans# G、㈣黃色殿、永久黃ncg、和撥、 Vulcan橙、陰丹士林、鮮橙GK、鐵紅、鮮洋紅6b、Frizaiii此 色澱、甲基紫色澱、永久紫B、鈷藍、鹼藍色澱、酞青藍、 堅牢天藍、顏料綠B、孔雀石綠色澱、氧化鈦和鋅白。以 1〇〇為置份的本發明的用於電子照相的調色黏合劑計，著 色劑的用量爲5-25質量份。 另外，如有必要，在不影響本發明效果的前提下，可 以部分地加入下列物質，如聚乙酸乙稀酯、聚烯烴、聚酯、 聚乙烯醇縮丁醛、聚氨酯、聚酰胺、松香、改性松香、⑮· 烯樹脂、酚樹脂、脂族烴樹脂、芳族石油樹脂、固體石蠟、 聚烯烴石蠟、脂族醯胺石蠟、氣乙烯樹脂、苯乙烯-丁二 烯樹脂、苯並二氫η比喃茚樹脂、三聚氰胺樹脂或其他物質。 另外，可以適當地選擇使用任何常用的電荷控制劑， 如苯胺黑、季銨鹽、含金屬的偶氮染料和其他物質。以1〇〇 質量份的本發明的用於電子照相的調色黏合劑計，電荷控 制劑的用量通常爲0.1-10質量份。 可以使用目前常用的任何方法作爲用於本發明的電 _ 子知、相的調色Θ彳的I備方法。如將本發明的用於電子照相 的調色黏合劑、著色劑、電荷調節劑、石蠟和其他物質預 先混合後，混合物於加熱和熔融態下於雙軸捏合機中捏 合，冷卻後用粉碎機粉碎捏合的混合物，用空氣分級機再 進一步分級’通常收集粒子尺寸爲8-20μιη的粒子，用於 製備電子照相的調色劑。關於在雙軸捏合機中的加熱和熔 融條件，優選雙軸捏合機的釋放口的樹脂溫度小於165 17 !227384 C，V留時間少於i8〇秒；關於冷卻方法，優選用鋼帶冷 卻器等驟冷。 在根據上述方法製備的用於電子照相的調色劑中，本 發明的用於電子照相的調色黏合劑的用量爲5〇質量％或 5〇質量％以上，優選60質量％或60質量％以上。對其用 里；又有上限，但根據本發明的目的，其用量通常最大爲 90-100 質量％ 。 根據下面的測試方法，進行黏-彈性的測試。 黏-彈設備：STRESS TECH流變儀（Rheol0gica有 拳 限公司） 測試方式：振動張力控制 溫度範圍：50-200°C 加熱速率·· 2°C/min 頻率·· 1Hz Gap : 1mm 平板：平行板 應力張力；1% # 實施例 根據下面的實施例具體地描述本發明，但本發明並不 限制於這些實施例。而且，除非有特殊地說明，否則下面 的’’份，，表示質量份。 含縮水甘油基的乙稀基樹脂（A )的製備實施例 製備實施例A-1 將75份的二甲苯放入燒瓶中並加熱，其中用氮氣置 18 !227384 換燒瓶内的空氣，將預先混合並溶解的05份苯乙烯、30 份丙烯酸正丁酯、5份甲基丙烯酸縮水甘油酯和1份的 過氧化一叔丁基的溶解混合物在二甲苯回流的狀態下，連 續加入5小時，再回流1小時。内部溫度保持爲130°C， 殘留的單體在2小時内聚合兩次，完成聚合反應。結果， 知到聚合液體。在溫度爲16(rc、壓力爲1〇mmHg的容器 中閃蒸該液體，以便除去溶劑等物質。製備的乙烯基樹脂 的物理性能的數值列於表1中。 製備實施例A-2 除了過氧化二叔丁基的用量從1份變爲0.4份，甲基 丙烯酸縮水甘油酯的用量從5份變爲13份，苯乙烯的用 量從65份變爲57份外，其他按與製備實施例a-Ι相同的 方法製備乙浠基樹脂。製備的乙烯基樹脂的物理性能的數 值列於表1中。 製備實施例A-3 將50份的二甲苯放入燒瓶中並在油浴中加熱，其中 用氮氣置換燒瓶内的空氣，將68份苯乙烯、27份丙烯酸 正丁 S曰、5伤甲基丙稀酸縮水甘油S旨和4份的過氧化二 叔丁基的溶液在二甲苯回流（内部溫度爲l38〇c )的狀態 下’連續地滴入5小時，然後聚合反應再進行1小時，加 入0.5份的過氧化二叔丁基，在内部溫度保持爲i3(rc的 條件下，反應再進行2小時，直到聚合反應結束。 製備的乙烯基樹脂的物理性能的數值列於表1中。 [含羧基的乙烯基樹脂（B)的製備實施例] 19 1227384 製備實施例B-l 將母100份苯乙烯中的〇·6份的過氧化二叔丁基均勻 地溶解於包括57.4份苯乙烯、η·9份丙烯酸正丁酯、〇.7 伤甲基丙烯酸和30份的二甲苯的溶液中形成的混合物 連績地按750cc/hr的速率加入到5升容器中，在内部溫度 爲190°C、壓力爲6kg/cm2的條件下進行聚合，製得低分 子量的聚合液體。 分別將75份苯乙浠、235份丙烯酸正丁酯、15份甲 基丙烯酸乙烯基單體放入燒瓶中，用氮氣瓶中的空氣，内 部溫度升高到12(TC，在該溫度下本體聚合10小時。此時 聚合的轉化率爲51%。然後，加入50份二甲苯，將預先 混合和溶解的O.i份的過氧化二叔丁基和5〇份的二曱苯 溶液連續地加入8小時，内部溫度保持爲i30°c的條件 下’殘留的單體再聚合2小時，直到聚合反應結束。結果， 製得高分子量的聚合液體。 然後，將上述的100份的低分子量的聚合液體和60 份上述的高分子量聚合液體混合，在溫度爲160°c，壓力 爲lOmmg的容器中閃蒸混合物，以便除去溶劑等物質。 製備的乙浠基樹脂的物理性能的數值列於表1中。 製備實施例B-2 除了苯乙稀的用量從57.4份變爲54.6份，甲基丙烯 酸的用量從0·7份變爲3.5份，以製備製備實施例中 的低分子量聚合液體量外，其他按製備實施例Β-1的相同 方法製備乙烯基樹脂。製備的乙烯基樹脂的物理性能的數 1227384 值列於表1中。 製備實施例B-3 除了苯乙烯的用量從57.4份變爲50.4份，丙烯酸正 丁醋的用量從11.9份變爲18.9份，以製備製備實施例 中的低分子量聚合液體量外，其他按製備實施例的相 同方法製備乙烯基樹脂。製備的乙烯基樹脂的物理性能的 數值列於表1中。 製備實施例B-4 將100份二甲苯加入燒瓶中並用油浴加熱，其中用氮 氣置換瓶内的空氣，然後將82份苯乙烯、17份丙烯酸正 丁酯、1份甲基丙烯酸和3份過叔丁基2-乙基己酸酯在 二甲苯回流下在5小時内連續地滴入（内部溫度爲138 °C )。聚合反應進行1小時後，加入0.3份的過叔丁基2_ 乙基己酸酯，反應再進行1小時，再加入0.5份的過叔丁 基2-乙基己酸酯，在内部溫度爲98°C的條件下，聚合反 應再進行2小時。製得低分子量的聚合液體。 分別將74份苯乙烯和23.5份丙烯酸正丁酯加入燒瓶 中，其中用氮氣置換瓶内的空氣，内部溫度保持爲12(TC 的條件下，用油浴中加熱，本體聚合6小時，此時本體聚 合的轉化率爲40%。本體聚合後，加入50份的二甲苯和 2.5份的曱基丙烯酸，在溫度保持爲ll〇°C的條件下，在9 小時内連續地滴入0.34份1’ 1-一（過叔丁基）3，3,5_ 三甲基環己烷和60份的二甲苯的溶液。聚合反應再進行2 小時後，加入0.2份的過氧化二叔丁基，反應再進行2小 21 1227384 時，再加入0.5份的過氧化二叔丁基，在内部溫度爲130 它的條件下，此後，反應再進行2小時，然後用123.33 份的二甲苯稀釋反應混合物，聚合反應結束。結果，製得 高分子量聚合液體。 然後，將上述的100份的低分子量的聚合液體和70. 3 份上述的高分子量聚合液體混合，在溫度爲190°C，壓力 爲lOmmHg的容器中閃蒸該混合物，以便除去溶劑等物 質。製備的乙烯基樹脂的物理性能的數值列於表1中。 實施例1 將製備實施例A-1中製備的3份乙烯基樹脂和製備實 施例B-1中製備的97份乙烯基樹脂在Henschel混合器中 混合，在雙軸捏合機（KEXN S-40型，由Kurimoto有限 公司製造）中捏合混合的樹脂，以便進行反應，其中雙軸 捏合機的排放口的樹脂溫度爲170°C，停留時間爲90秒， 然後將捏合産品冷卻並研磨，以製備用於電子照相的調色 黏合劑。用鋼帶冷卻器作爲冷卻方法，其中冷卻水溫度爲 l〇°C，用量爲每1公斤樹脂20升的冷卻水（* )的條件下， 以0.08kcal/mhrs的熱傳導率驟冷捏合産品。製備樹脂的 各種各樣的條件和其物理性能的數值列於表1中。然後， 將6份的碳黑、REGAL (商標名）330R (由CABOT公 司製造），2.5份的聚丙烯石蠟，NP105(由三井化學公司生 産）和1份的Bontron S34(由Orient化學工業有限公司生産） 的電荷調節劑加入樹脂中，在Henschel混合機中混合，並 在雙軸捏合機（PCM-30型，Ikekai，Kikai有限公司製造） 22 1227384 中^ 口 ’其中雙轴捏合機的排放口的樹脂溫度爲150°C， τ邊日寸間爲30秒。然後捏合的産物進行冷卻、研磨、分 、、、製備尺寸約爲7微米的用於電子照相的調色劑。冷 飞方法與上述的驟冷法相同。如上所述，*表示質量份，3 伤的電子照相調色劑和97份的載劑混合，以製備顯影劑。 更換市售的南速影印機，根據影印機複印的圖像質量來評 價顯影劑，其結果列於表i中。 實施例2 除了雙軸捏合機的排放口的樹脂溫度爲185°C外，其鲁 他按與實施例1的相同方法進行。製備樹脂的各種各樣的 條件和其物理性能的數值列於表1中。 實施例3 除了製備實施例中製備的乙烯基樹脂爲7份，製 備實施例B_1中製備乙烯基樹脂爲％份外，其他按與實 施例2的相同方法進行。製備樹脂的各種各樣的條件和其 物理性能的數值列於表1中。 實施例4 φ 除了雙軸捏合機的排放口的樹脂溫度爲2〇〇〇c，停留 時間爲3〇秒外，其他按與實施例1的相同方法進行。製 備樹脂的各種各樣的條件和其物理性能的數值列於表工 中。 ' 實施例5 除了製備實施例A-1中製備的乙烯基樹脂變爲製備實 施例A-2中製備乙烯基樹脂外，其他按與實施例2的相同 23 1227384 方法進行。製備樹脂的各種各樣的條件和其物理性能的數 值列於表1中。 ' 貫施例6，7 除了製備實施例B-1中製備的乙烯基樹脂變爲製備實 YJ B 2 (相應於實施例6 )和B-3 (相應於實施例7)中 製備的乙烯基樹脂外，其他按與實施例2的相同方法進 行。製備樹脂的各種各樣的條件和其物理性能的數值列於 表1中。 > _ 實施例8 除了製備實施例A-2中製備的乙烯基樹脂和製備實施 例B-1中製備的乙烯基樹脂的混合比爲97/3外，其他按 與實施例1的相同方法進行。製備樹脂的各種各樣的條件 和其物理性能的數值列於表1中。 實施例9 除了製備實施例A-1中製備的乙烯基樹脂和製備實施 例B-1中製備的乙烯基樹脂的混合比爲從97/3變爲94/6 鲁 外，其他按與實施例2的相同方法進行。製備樹脂的各種 各樣的條件和其物理性能的數值列於表i中。 實施例10 _ 將製備實施例B-4中製備的93份乙稀基樹脂和製備 · 實施例A-3中製備的7份乙烯基樹脂在Henschel混合器 中混合，此合树脂在雙軸捏合機（Kexn S40型，由 kunmoto有限公司製造）中捏合混合樹脂，以便進行反 24 1227384 應’其中雙軸捏合機的排放口的樹脂溫度爲185。〇，停留 曰守間爲90秒，然後將得到的樹脂冷卻並用研磨機（power mill p_3型，由Sanei Fact〇ry公司製造）研磨，以製備用於 電子照相的調色黏合劑。冷卻方法與實施例1中的驟冷方 法相同。然後，將6份碳黑、REGAL (商標名）330R(由 CABOT公司製造），2.5份的聚丙烯石蠟，Νρι〇5(由三井 化學公司生産）和1份的Bontron S34(由Orient化學工業有 限公司生産）的電荷調節劑加入樹脂中，在Henschel混合 機中混合，並在雙軸捏合機（PCM_3〇型，由Ikegai，Kikai · 有限公司製造）中捏合，其中雙軸捏合機的排放口的樹脂 度度爲155 C，停留時間爲60秒。然後捏合産物進行冷 卻、研磨、分級，以製備尺寸約爲7微米的用於電子照相 的調色劑。冷卻方法與上述實施例i中的驟冷法相同。3 份用於電子照相調色劑和97份的載劑混合，以製備顯影 劑。更換市售的高速影印機，根據影印機複印的圖像質量 來評價顯影劑’測試製備得到的用於電子照相的調色黏合 劑的黏-彈性的測量結果列於圖4中。製備樹脂的各種各鲁 樣的條件和其物理性能的數值列於表1中。 比較實施例1 除了捏合反應在雙軸捏合機的排放σ的樹脂溫度爲 2賦，停留時間爲90秒的條件下進行外，其他按與實施 例1的相同方法進行來製備調色黏合劑。除了使用該實施 例中製備的調色黏合劑外，其他按與實施例ι的相同方法 製備和評價調色劑。測試樹脂的各種各樣的條件和其物理 25 1227384 性能的數值列於表2中。 比較實施例2 除了雙軸捏合機的排放口的樹脂溫度爲22〇aC外，其 他按與比較實施例1的相同方法進行。製備樹脂的各種各 樣的條件和其物理性能的數值列於表2中。 比較實施例3 除了製備實施例A-1中製備的乙烯基樹脂爲7份和製 備實施例B-1中製備的乙烯基樹脂爲93份外，其他按與 比較實施例1的相同方法進行。製備樹脂的各種各樣的條修 件及其物理性能的數值列於表2中。 比較實施例4 除了停留時間爲180秒外，其他按與比較實施例1的 相同方法進行。製備樹脂的各種各樣的條件及其物理性能 的數值列於表2中。 比較實施例5 除了製備實施例A-1中製備的乙烯基樹脂變爲製備實 施例A-2中製備的乙浠基樹脂的外，其他按與比較實施例 H 1的相同方法進行。製備樹脂的各種各樣的條件及其物理 性能的數值列於表2中。 比較實施例6，7 除了製備實施例B-1中製備的乙烯基樹脂變爲製備實 施例B-2 (相應於比較實施例6 )和B-3 (相應於比較實施 例7)中製備的乙烯基樹脂的外，其他按與比較實施例1 的相同方法進行。製備樹脂的各種各樣的條件及其物理性 26 1227384 能的數值列於表2中。 比較實施例8 除了製備實施例A-2中製備的乙烯基樹脂和製備實施 例B-1中製備的乙稀基樹脂的混合比爲97/3外，其他按 與比較實施例1的相同方法進行。製備樹脂的各種各樣的 條件及其物理性能的數值列於表2中。 比較實施例9 除了製備實施例A-1中製備的乙烯基樹脂和製備實施 例B-1中製備的乙烯基樹脂的混合比從97/3變爲94/6 外，其他按與比較實施例1的相同方法進行。製備樹脂的 各種各樣的條件及其物理性能的數值列於表2中。 比較實施例10 除了捏合反應在雙轴捏合機的排放口的樹脂溫度爲 220 C，停留時間爲180秒的條件下進行外，其他按與實 施例10的相同方法進行來製備調色黏合劑。除了使用該 實她例中製備的調色黏合劑外，其他按與實施例1〇的相 同方法製備調色劑。製備的調色黏合劑的黏_彈性的測試籲 結果列於圖4中。製備樹脂的各種各樣的條件及其物理性 能的數值列於表2中。 調色劑的評價方法 1)定影性能1227384 Description of the invention: [Technical field to which the invention belongs] The present invention relates to a toning adhesive for electrophotography, which is used to develop electrostatic charge images by electrophotography, electrostatic recording, electrostatic printing, and the like. 'The present invention relates to a toner for electrophotography, which is used in a high-speed photocopier, has high resolution, good image quality, and has excellent grindability. [Prior art] Electrophotographic methods are commonly used in PPC photocopiers or printing presses, in which a toned image is formed on a photoconductor and then transcribed onto a recording paper (Plain Paper Copy Method), so that an electrostatic latent image is formed on the photoelectric The conductor is then used to develop a latent image with toner, and the toned image is transcribed onto a fixed print such as paper or a similar print, and heated with a heating roller to fix the transcribed image. Because fixing under heat and pressure, this method can be performed quickly, and the thermal efficiency is very high, so the fixing efficiency is also very high. Although the heating roller method has good thermal efficiency, when the toner is in a molten state, the toner is in contact with the surface of the heating roller. Under the adhesion, the toner is transferred to the surface of the heating roller, and the transferred toner It is then transferred to a fixed bottom-print, which stains the print (offset phenomenon). Machine installation is not advisable. Applying Shixi oil to the surface of the heating roller with cloth or paper can prevent the occurrence of offset. Although this method is effective in preventing toner offset, it requires a kind of equipment to supply liquid to prevent offset, and the maintenance and administration are complicated, so the cost is high. Such materials are easy to volatilize, so this square hair will get the inside of 1227384 dirty machine. Kou Eri hopes to develop a research-type toner for high-speed machines (oil-free fixing method). In this method, it is not necessary to apply the above-mentioned Shixi oil and the like: (oil-free fixing method). In addition, when the photocopier is pointed at a high speed, the speed of the fixing roller must be reported to the south, and the toner must be fixed by heating in a short time. To make the toner in a molten state in a short time, the fluidity must be high. Although lowering the glass transition temperature (hereinafter referred to as _U) of the resin used as the toner can effectively improve the fixing performance, undesirable phenomena such as toner agglomeration often occur during storage. ... in addition, there have been many methods of using a crosslinked polymer to prevent the toner from shifting in the oil-free shadowing method. For example, Japanese Patent Laid-Open No. 6 () _ 36582 discloses a method using a crosslinked polymer prepared by an emulsion polymerization method. In this method, the crosslinked polymer used contains 5% by mass of gel. Increasing Rishou 'in a improves the offset resistance, but the grindability becomes worse, and when the content of glue is decreased, the grindability is improved, but the offset resistance decreases. It is difficult to improve offset resistance and abrasion resistance at the same time. "In the method, when preparing a crosslinked polymer, a dispersant or dispersing aid must be used at the same time in order to stabilize the emulsified particles. However, these dispersions = high absorption, high performance, and severely affect its electrical properties, especially charge stability. After the preparation of the coupling polymer, it is necessary to remove as much of the dispersed labor as possible, and the amount of drainage and treatment is also very large. In addition, a method is disclosed in USP 4,966,829, in which an ethylene-containing polymer is used. The toner has a better effect. The ethylene-based polymer contains 1227384 0.1% by mass of gel. In the soluble portion of tetrahydrocrack, the molecular weight of the main peak is MOO-25,000, and at least one Sub-peaks or spikes with molecular weights ranging from 3 to 0-150,000. However, since the method for preparing this polymer is a 4 float solution polymerization method, which is similar to the emulsion polymerization method, a dispersion sword or a dispersing aid must be used at the same time. The above-mentioned emulsion polymerization method has the same problem. In order to solve the above-mentioned problem, the inventors have developed a resin prepared by a solution polymerization method. The resin can be used as a toner having good fixability (USP No. 4 , 963, 456). In the resin prepared by the solution polymerization method, Yuling d is removed after the polymerization is completed. At this time, all low-boiling components can be removed, including unreacted residual monomers and decomposition products of the initiator. The best resin as a toner is a homogeneous resin containing a small amount of impurities and stable electrical properties. However, when the cross-linked polymer is prepared by the solution polymerization method, 'because of the Weissenberg effect (the resin is wound on a stirring rod), It is difficult to prepare a cross-linked polymer. Therefore, the present inventor has also developed a method for preparing a polymer having a molecular weight as high as possible by using a method such as bulk polymerization (USP No. 5,084,368). However, the molecular weight of the prepared polymer is limited. Therefore, the disadvantage of offset is not completely overcome. _ In addition, Japanese Patent Gazette No. 60-38700 discloses a copolymer (A) and cross-linking by heating and mixing a glycidyl group-containing 3 to 40% monomer. The coloring adhesive prepared by the compound (B) has a better effect, but the color life of this coloring agent is limited. In the long-term test, because there are many epoxy residues, an oppositely charged Moreover, the present inventors have also studied a method for preparing a toner with excellent properties by cross-linking a resin and a compound with a certain ratio, wherein the resin described in 1227384 contains several groups prepared by a solution polymerization method, and The compound contains a glycidyl group (Japanese Patent Laid-Open Publication Nos. 006, 89, and 22612). The toner prepared by an illegal method can be used in a high-speed machine. Good balance, and good grindability, electrical properties and charge stability, and high kink ratio. However, during the kneading process of toner preparation, when the cross-linking component is subjected to excessive shearing to cut the gel ' At high temperatures, the elasticity of the toner is insufficient so that the quality of the image becomes poor after fixing, and * a sufficient offset effect can be obtained. The present inventors have earnestly studied in order to meet the necessary requirements of the above requirements ^ and thus developed a method for preparing a color-grading adhesive by improving the molecular neutralization and oxygen value of a glycidyl-containing crosslinking agent. (Japanese Patent Laid-Open Publication No. 09-31914). The prepared hueing adhesive can reduce the cutting effect of the gel during the kneading process of preparing the hueing toner, and has good continuous development and anti-offset properties, while greatly improving the fixability, anti-offset properties and The balance between agglomeration, and also has excellent scalability, production efficiency, electrical performance and charge stability. But the 'Muli market needs new technologies that save energy and speed. Therefore, it is necessary to reduce the heating time through high-speed technology, thereby reducing the fixing temperature, and reduce the fixing temperature through energy saving. However, when the temperature is further lowered, the conditions for satisfying the fixability are very severe. Therefore, it is difficult to satisfy the conditions for further lowering the fixability and the offset resistance at the same time by the above method. [Summary of the Invention] In order to meet the needs of the high speed and energy saving of the photocopier market, while improving the fixability at low temperature and the balance between fixability and offset resistance, an object of the present invention 1227384 is to improve the adjustment for electrophotography All properties of the toner, including fixability, anti-offset properties, blocking properties, grindability, and continuous development. The present inventors have earnestly studied these necessary conditions for meeting the above-mentioned needs, and found that, when preparing a coloring adhesive for electrophotography by cross-linking a cross-linking compound and a copolymer, the cross-linking reaction is stopped during the reaction to Preparation of low-viscosity coloring adhesives to improve the fixability. During the fixing process, the cross-linking reaction is continued using the remaining cross-linking activity, thereby improving the offset, while improving the grindability, agglomeration and continuous development . A technology for preparing a toning adhesive for electrophotography has been completed, which is used in a high-speed printing press, and has excellent fixability, offset resistance, agglomeration, abrasion resistance, and continuous development, at 140 In the range of -180 ° C, the visco-elastic curve is concave, where the bottom end of the curve represents the minimum value of 0 □ 〇, and the minimum value GOO and the storage modulus G at 200 ° C are also specifically expressed. The difference between 200. _ The invention is described in detail below. (1) A toning adhesive for electrophotography, in which the visco-elasticity of the toning adhesive is measured at a heating rate of 2 ° c / min in the range of 50 to 200 ° C. 100-200X: The visco-elastic curve in the range shows the relationship between storage modulus and temperature, where the ordinate of the curve is the logarithm (pa) of storage modulus G and the abscissa is temperature (it), at 14 _18〇. 〇Range · When the curve is concave, the bottom end of the curve represents the minimum value of the storage modulus G, and the relationship between G G ′ ′ and the storage modulus G at 200 ° C is 200. < G, 200, and the difference ΔG, (G, 200_G, 〇 = Ag,) is 300 Pa or 300 Pa or more. 9 1227384 (2) The toning adhesive for electrophotography according to (1), wherein the value of the storage modulus at 200 ° C is 1000 Pa or more. (3) The hueing adhesive for electrophotography according to (1) or (2), wherein the hueing adhesive has a glass transition temperature of 45-75 ° C and contains 0.1-20% by mass of gel. Glue has a peak in the molecular weight range of 40,000 to 50,000. The molecular weight distribution is determined by gel permeation chromatography based on the soluble portion of the hueing binder in tetrahydrofuran. (4) The hueing adhesive for electrophotography according to any one of (1) to (3), wherein the degree of crosslinking reaction is U0%. (5) The toning adhesive for electrophotography according to any one of (1) to (4), wherein the toning adhesive is a vinyl resin (A) containing a glycidyl group by heating and melting, and Prepared by a carboxyl group-containing vinyl resin (b), the vinyl resin (A) has a weight average molecular weight of 10,000-100,000, an epoxy value of 0.0005-〇1Eq / 1OOg, and a resin (B) It has an acid value of 1-30 mgKOH / g and a glass transition temperature of 40-7000 c. For crosslinking, the above-mentioned glycidyl group-containing ethylene resin (A) is used as a crosslinking agent. (6) The toning adhesive for electrophotography according to any one of (1) to (5), wherein one resin of styrene-acrylic resin is used as a main component. (7) A toner for electrophotography, wherein the toner adhesive for electrophotography according to any one of (1) to (6) above is used. 1227384 [Embodiment] ~ The glycidyl group-containing vinyl resin (A) of the present invention is prepared by copolymerizing a glycidyl group-containing vinyl monomer and another vinyl monomer as a glycidyl group-containing Ethylene resin ⑷, preferably the polymer has a weight average molecular weight in the range of 10, __1〇〇, _, more preferably M, surface _ 85,000, most preferably 25, _ 75, _, epoxy value is 0. 〇, iEq / 100g, measured according to JISK7236 standard. If the weight-average molecular weight is less than ιο'οοο, the gel is easily sheared during the kneading process for preparing an electrophotographic toner, and after fixing, the continuous developability and offset resistance are reduced; 隹 If the weight-average molecular weight is greater than 100,000 , Poor fixability. The epoxy value is preferably in the range of 0.001 · 0.1 Eq / 100 g. If the epoxy value is less than 0.0005 Eq / 100g, the production amount and offset resistance of the gel are reduced; if the epoxy value is greater than ο · 1 'during the kneading process of the toner for preparing an electrophotographic, the gel Easily be bravely 'continuously developability and anti-offset resistance decrease. The carboxyl group-containing vinyl resin (B) of the present invention is prepared by copolymerizing a vinyl group-containing vinyl monomer and other vinyl monomers. The acid value of the carboxyl group-containing vinyl resin (B) is preferably in accordance with JISk54. 〇7 · Standard measurement. Tg is 40-70 ° C and measured according to JIS K7121. More preferably, the acid value is 5-25 mg KOH / g, and the Tg is 50-6 (TC. If Tg is less than 40 ° C, it is easy to agglomerate; if Tg is more than 70 ° C, the softening point is increased, and the fixability is deteriorated. If the acid value is less than 1 mg KOH / g, the reaction amount per molecule is low, and the molecular weight is difficult to increase; if the acid value is more than 30 mg KOH / g, the gelation is easy during the kneading process for preparing an electrophotographic toner. It is cut, and the continuous development property and offset resistance are reduced. 11 1227384 The toning adhesive for electrophotography of the present invention is obtained by heating and melting the glycidyl group-containing vinyl resin (A) and the crosslinked resin. Prepared by Weickey's vinyl resin (B), the toning adhesive contains G.l-20% gel, preferably 1-2G%, more preferably. If the percentage of gel in the toning adhesive for electrophotography If it is less than 0.1%, it is difficult to have offset resistance. If the percentage of the gel group is greater than 20%, the fluidity is reduced, the temperature is low, and the fixing property is deteriorated. It is difficult to use it in a high-speed photocopying machine. It is also preferable to use a glycidyl group-containing vinyl resin (A) and a carboxyl group-containing vinyl resin (B) for the crosslinking reaction, The glycerol content in the glycerol group is 0.01-1 · 0 equivalents, preferably 0.008 g equivalents, and each gram equivalent of the carboxyl group is equivalent to a glycidyl group. In the present invention, a glycidyl group-containing Examples of the glycidyl-containing vinyl monomer used in the vinyl resin (A) are, for example, glycidyl acrylate, non-methyl glycidyl acrylate, glycidyl methacrylate, and methacrylic stone-formaldehyde Glycidyl methacrylate, etc., but glycidyl methacrylate and methyl glycidyl methacrylate are preferred. These glycidyl group-containing vinyl monomers can be used alone or in combination of two or more kinds. Examples of the carboxyl group-containing vinyl monomer (including an anhydride of an unsaturated polycarboxylic acid) used in the preparation of the carboxyl group-containing vinyl resin (B) in the present invention are, for example, monoesters of unsaturated dibasic acids, including acrylic acid , Methacrylic acid, maleic anhydride, maleic acid, fumaric acid, monoesters of cinnamic acid, methyl fumarate, ethyl succinate, propyl succinate, butyl fumarate, fumarate Octyl ester, maleic acid Intended purpose, ethyl maleate, propyl maleate, butyl maleate, and male 12 1227384 octyl maleate, preferably acrylic acid, methacrylic acid, fumaric acid monoester, fumaric acid methyl ester 6 The ethyl δ fumarate, the propyl fumarate, the butyl fumarate, and octyl fumarate. These carboxyl group-containing vinyl monomers can be used alone or in combination of two or more. Examples of ethylene precursors copolymerized with a glycidyl vinyl monomer and a carboxyl group-containing vinyl precursor include styrene, p-methylstyrene, and α-methylstyrene; Acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl propionate, cyclohexyl acrylate, acrylic stearate, benzyl acrylate, furfuryl propionate, hydroxy acrylate Ethyl esters, hydroxybutyl acrylate, dimethylaminomethyl acrylate, and methylaminoethyl acrylate; methyl acrylates include methyl methacrylate, ethyl methacrylate, Propyl methacrylate, butyl methacrylate, octyl methacrylate, methyl Cyclohexyl enoate, stearate methacrylate, benzyl methacrylate, furfuryl methacrylate, hydroxyethyl methacrylate, hydroxybutyl methacrylate, dimethylcarbamate methacrylate Esters and dimethylaminoethyl methacrylate; diesters of unsaturated dibasic acids include dimethyl fumarate, dibutyl fumarate, dioctyl fumarate, dimethyl maleate, Dibutyl maleate, dioctyl maleate; and amidines include acrylonitrile, methacrylonitrile, acrylamide, acrylamide, N-substituted acrylamide, and N-substituted Methacrylamide; Among these vinyl monomers, at least one vinyl monomer is used. Among these, particularly preferred monomers include ethylene, acrylate, methacrylate, dialkyl fumarate, acrylonitrile, acrylamide, amidinoacrylamide, and the like. These vinyl monomers may be used alone or in combination of two or more. 13 1227384 The number average molecular weight and the weight average molecular weight are comparative molecular weights measured by GPC (gel permeation chromatography), and a calibration curve is prepared using a monodisperse standard polystyrene edge. The test conditions are as follows: GPC equipment; JASCO TWINCLE HPLC detector; SHODEX RI SE-31 column; SHODEX GPCA-80M * 2 + KF-802 solvent; Tetrahydrocran flow rate; 1.2ml / min of gel fraction of the present invention The percentage is determined based on the values tested below. After putting 2.5 g of resin and 47.5 g of ethyl acetate into 100 ml of the sample tester, and stirring at 22 ° C for 12 hours at a speed of 50 rpm, the sample test tube was at 22 ° Cf, Let stand for 12 hours. Then, 5 g of the supernatant in the sample test tube was dried at 15 (rc for 1 hour, the mass of the product (Xg) was weighed, and the percentage of gel was calculated according to the following formula. Gel (%) = {(2.5 / 50 -X / 5) / (2 5 / 5〇)} χ100. With regard to the preparation of a toner adhesive for electrophotography using the polymers (A) and (B) of the present invention, the following method and the like can be used Method, # wherein the polymer (B) is a silk-containing vinyl resin (B), and the polymer (A) is a glycidyl-containing vinyl resin (a). The glycidyl-containing vinyl resin (A) Mix with silk-containing ethylenic resin H in a Hensehel mixing ， container, melt in a biaxial kneader, and knead it for a cross-linking reaction with a money base and a glycidyl group. • In resin (A) and resin fd, CB) in the cross-linking reaction, stop the cross-linking reaction, use the residual cross-linking method to make μ′-linking, tongue preparation 14 1227384 agent for electrophotography to prepare according to this method The hueing adhesive has a low viscosity, thereby improving its fixability. In addition, in the cross-linking reaction, when the cross-linking reaction is completed (this is expressed by the gel content of the complete reaction), the gel content is 15%, preferably 5-45%. Cross-linking activity (This is expressed by the degree of cross-linking reaction, and the degree of cross-linking reaction (gel (%) / fully-reacted gel (%) χΐ〇〇) is determined according to the following general formula.) The cross-linking reaction is continued. For the purpose, it is preferable that the resin temperature of the release port of the biaxial kneader is 165 ° c -19 (below rc, the residence time is 90 · 80 seconds, and the resin is melted and kneaded. When the resin temperature of the release port of the biaxial kneader is, In the range of 190-200 °, the residence time is less than 90 seconds. In addition, when the resin temperature at the discharge port of the biaxial kneader is 22 ° C, and the kneading time is within 180 seconds, the gel content is defined. It is the gel content when the crosslinking reaction is completed, that is, the gel content of the complete reaction. The resin prepared by this method is cooled and ground to prepare a toning adhesive for electrophotography. Although currently commonly used cooling and Grinding method 'but steel strips etc. are preferred A method for cooling a substance by quenching the resin. The method for melting and kneading the resin (A) and the resin (B) in the present invention to carry out a cross-linking reaction can be a heating and melting resin method commonly used at present, but is preferred Method using a biaxial kneader. The electrophotographic tinting adhesive prepared according to the present invention was tested for visco-elasticity under the conditions of a temperature range of 50 ° C to 200 ° C and a temperature increase rate of 2 ° C / min. · The visco-elastic curve in the range of 100-200 ° C represents the relationship between storage modulus and temperature, the ordinate of the curve represents the logarithm of the storage modulus G > (Pa), and the abscissa represents the temperature (° C), In the range of 140-180 ° C, the visco-elastic curve is 15 1227384 concave. The bottom end of the curve represents the minimum value of storage modulus G > 〇, the storage modulus G / 200 is preferred at a temperature of 200c. The relationship between the storage modulus at 200 is 50,000 Pa, more preferably 2,000 to 40,000 Pa, and most preferably 20,000 20,000 Pa, G / 〇 and 2000. ( } / 0 < 200, and the difference △ G (G 200_ G / 〇 = △ g-) is preferably 30,000, 000pa, more preferably 400,000 to 40,000pa, and most preferably 50,000,000pa . If the storage modulus G 200 is less than 1,000 Pa, the viscosity decreases at high temperatures, and it is difficult to provide sufficient offset resistance. And if △ G, < 3〇00pa, 疋 ~ [It is difficult to balance health and offset resistance. Although the fixability is good at low temperatures, it is difficult to achieve a balance between the fixability and the offset resistance. In addition, the butyl name of the toning adhesive for electrophotography of the present invention is preferably 45 to 751, more preferably 45 to 70. 〇, most preferably 50-pits, the molecular weight range of the soluble portion of tetrahydrofuran in the toning adhesive for electrophotography in the above f is preferably 4,005,00,00, More preferably, it is 0,40G ', most preferably 8,3G, and the molecular weight distribution measured by gel permeation chromatography (GPC) is deleted. Eight ^ ^ ^ less than 45 C 'Easily agglomerated' If the Tg is greater than 75 ° C or the peak value in the zirconia exceeds 50,000, the resin becomes hard and the fixability becomes poor. If the peak value of the sub-quantity is less than 4,000, the offset phenomenon is liable to occur. Toners for electrophotography can be prepared by the known methods using the toning agent and coloring agent for electrophotography of the present invention. If necessary, charge control agents, release agents, and pigments can be used. Dispersant. Examples of such toners are: black pigments including carbon black, ethyl black, lamps ... and magnetite; chrome yellow; yellow iron oxide; and commonly used organic and inorganic! 227384 pigments include Hans # G 、 ㈣ 黄 殿, Permanent yellow ncg, and dial, Vulcan orange, indanthrene, fresh orange GK, iron red, fresh magenta 6b, Frizaiii this lake, methyl violet lake, permanent violet B, cobalt blue, alkali blue lake, phthalocyanine Blue, fast sky blue, pigment green B, malachite green lake, titanium oxide and zinc white. The toner is used in an amount of 5 to 25 parts by mass based on the toner-adhesive for electrophotography of the present invention based on 100 parts. In addition, if necessary, without affecting the effects of the present invention, the following substances can be partially added, such as polyvinyl acetate, polyolefin, polyester, polyvinyl butyral, polyurethane, polyamide, rosin, Modified rosin, fluorene resin, phenol resin, aliphatic hydrocarbon resin, aromatic petroleum resin, solid paraffin, polyolefin paraffin, aliphatic ammonium paraffin, gas vinyl resin, styrene-butadiene resin, benzodiene Hydrogen η than indane resin, melamine resin, or other substances. In addition, any commonly used charge control agents such as aniline black, quaternary ammonium salts, metal-containing azo dyes, and other materials can be appropriately selected and used. The amount of the charge-controlling preparation is usually 0.1 to 10 parts by mass based on 100 parts by mass of the toner adhesive for electrophotography of the present invention. Any method commonly used at present can be used as the preparation method of the electronic and phase toning θ 彳 used in the present invention. For example, after the toning adhesive, coloring agent, charge regulator, paraffin, and other substances for electrophotography of the present invention are mixed in advance, the mixture is kneaded in a biaxial kneader under heating and melting, and then cooled using a pulverizer The kneaded mixture is pulverized, and further classified with an air classifier. Particles having a particle size of 8-20 μm are usually collected, and are used to prepare an electrophotographic toner. Regarding the heating and melting conditions in the biaxial kneader, it is preferred that the resin temperature at the release port of the biaxial kneader is less than 165 17! 227384 C, and the V residence time is less than 80 seconds; as for the cooling method, a steel belt cooler is preferred And so on. In the toner for electrophotography prepared according to the above method, the amount of the toner binder for electrophotography of the present invention is 50% by mass or more, preferably 60% by mass or 60% by mass. the above. There is an upper limit, but according to the purpose of the present invention, the amount is usually 90-100% by mass. The visco-elasticity test was performed according to the following test method. Visco-elastic equipment: STRESS TECH rheometer (Rheol0gica Youku Co., Ltd.) Test method: Vibration tension control Temperature range: 50-200 ° C Heating rate · 2 ° C / min Frequency · 1Hz Gap: 1mm Flat plate: Parallel Sheet stress tension; 1% # Examples The present invention is specifically described based on the following examples, but the present invention is not limited to these examples. In addition, unless otherwise specified, the following '' parts represent mass parts. Preparation Example of Glycidyl Group-Containing Ethylene Resin (A) Preparation Example A-1 75 parts of xylene was put into a flask and heated, wherein nitrogen was set to 18 227384 and the air in the flask was replaced. Mix and dissolve the dissolved mixture of 05 parts of styrene, 30 parts of n-butyl acrylate, 5 parts of glycidyl methacrylate, and 1 part of mono-tert-butyl peroxide under continuous reflux of xylene. Reflux for an additional hour. The internal temperature was maintained at 130 ° C, and the remaining monomers were polymerized twice in 2 hours to complete the polymerization reaction. As a result, a polymerization liquid was known. The liquid was flash-evaporated in a container at a temperature of 16 ° C and a pressure of 10 mmHg to remove substances such as solvents. The values of the physical properties of the prepared vinyl resin are listed in Table 1. Preparation Example A-2 The amount of di-tert-butyl oxide was changed from 1 part to 0.4 part, the amount of glycidyl methacrylate was changed from 5 to 13 parts, and the amount of styrene was changed from 65 to 57 parts. a-I The same method was used to prepare the acetamyl resin. The values of the physical properties of the prepared vinyl resin are shown in Table 1. Preparation Example A-3 50 parts of xylene was placed in a flask and heated in an oil bath. In which, the air in the flask was replaced with nitrogen, and a solution of 68 parts of styrene, 27 parts of n-butyl acrylate, 5-methyl methacrylic acid and 4 parts of di-tert-butyl peroxide in xylene Continuously dripping for 5 hours under reflux (internal temperature of 138 ° C), and then the polymerization reaction was continued for another 1 hour. 0.5 part of di-tert-butyl peroxide was added, and the internal temperature was maintained at i3 (rc). The reaction was continued for another 2 hours until the polymerization reaction was completed. The numerical values of the physical properties of the alkenyl-based resin are shown in Table 1. [Preparation Example of Carboxyl-Containing Vinyl Resin (B)] 19 1227384 Preparation Example Bl Peroxide of 0.6 parts of 100 parts of mother styrene was peroxidized. Di-tert-butyl was uniformly dissolved in a solution comprising 57.4 parts of styrene, η · 9 parts of n-butyl acrylate, 0.7 methacrylic acid, and 30 parts of xylene in a row of 750 cc / hr. The rate was added to a 5 liter container, and polymerization was performed under the conditions of an internal temperature of 190 ° C and a pressure of 6 kg / cm2 to obtain a low-molecular-weight polymerization liquid. 15 parts of vinyl methacrylic monomer was put into a flask, and the internal temperature was raised to 12 ° C with air in a nitrogen bottle, and bulk polymerization was performed at this temperature for 10 hours. At this time, the polymerization conversion rate was 51%. Then 50 parts of xylene was added, and the pre-mixed and dissolved Oi parts of di-t-butyl peroxide and 50 parts of dibenzobenzene solution were continuously added for 8 hours, and the internal temperature was maintained at i30 ° c under the condition of 'residual The monomers were polymerized for another 2 hours until the polymerization reaction was completed. Results A high molecular weight polymer liquid was prepared. Then, 100 parts of the above low molecular weight polymer liquid and 60 parts of the above high molecular weight polymer liquid were mixed, and the mixture was flash-evaporated in a container at a temperature of 160 ° C and a pressure of 10 mmg so that Removal of solvents and other substances. The values of the physical properties of the prepared acetamyl resin are shown in Table 1. Preparation Example B-2 Except for the amount of styrene being changed from 57.4 parts to 54.6 parts, the amount of methacrylic acid was changed from 0 · 7 parts were changed to 3.5 parts to prepare a vinyl resin in the same manner as in Preparation Example B-1 except for the amount of the low molecular weight polymerization liquid in Preparation Example. The physical properties of the prepared vinyl resin are shown in Table 1 in numbers of 1,227,384. Preparation Example B-3 Except that the amount of styrene was changed from 57.4 parts to 50.4 parts, and the amount of n-butyl acrylate was changed from 11.9 parts to 18.9 parts. A vinyl resin was prepared in the same manner as in the examples. The numerical values of the physical properties of the prepared vinyl resin are shown in Table 1. Production Example B-4 100 parts of xylene was added to a flask and heated with an oil bath, wherein the air in the bottle was replaced with nitrogen, and then 82 parts of styrene, 17 parts of n-butyl acrylate, 1 part of methacrylic acid, and 3 parts Per-t-butyl 2-ethylhexanoate was continuously dripped in under xylene reflux for 5 hours (internal temperature: 138 ° C). After the polymerization reaction was carried out for 1 hour, 0.3 parts of per-t-butyl 2-ethylhexanoate was added, and the reaction was further carried out for 1 hour. Then, 0.5 part of per-t-butyl 2-ethylhexanoate was added, and the internal temperature was 98. At a temperature of ° C, the polymerization reaction was continued for another 2 hours. A low molecular weight polymeric liquid was prepared. 74 parts of styrene and 23.5 parts of n-butyl acrylate were added to the flask, in which the air in the bottle was replaced with nitrogen, and the internal temperature was maintained at 12 ° C. and heated in an oil bath to polymerize for 6 hours. The conversion rate of the bulk polymerization was 40%. After the bulk polymerization, 50 parts of xylene and 2.5 parts of fluorenyl acrylic acid were added, and 0.34 parts of 1 were continuously added dropwise within 9 hours while maintaining the temperature at 110 ° C. 1 '1-mono (per-t-butyl) 3,3,5_ trimethylcyclohexane and 60 parts of xylene solution. After polymerization for another 2 hours, 0.2 part of di-tert-butyl peroxide was added and the reaction For 2 hours 21 1227384, add 0.5 parts of di-tert-butyl peroxide, and the internal temperature is 130. After that, the reaction is performed for another 2 hours, and then the reaction mixture is diluted with 123.33 parts of xylene to polymerize. The reaction was completed. As a result, a high-molecular-weight polymer liquid was prepared. Then, the above-mentioned 100 parts of the low-molecular-weight polymer liquid and 70. 3 parts of the above-mentioned high-molecular-weight polymer liquid were mixed, and the container was at a temperature of 190 ° C and a pressure of 10 mmHg. Flash the mixture in The solvent and other substances are removed. The values of the physical properties of the prepared vinyl resin are listed in Table 1. Example 1 Three parts of the vinyl resin prepared in Preparation Example A-1 and those prepared in Preparation Example B-1 were used. 97 parts of vinyl resin were mixed in a Henschel mixer, and the mixed resin was kneaded in a biaxial kneader (KEXN S-40 type, manufactured by Kurimoto Co., Ltd.) to perform a reaction in which the resin at the discharge port of the biaxial kneader The temperature was 170 ° C, the residence time was 90 seconds, and then the kneaded product was cooled and ground to prepare a toning adhesive for electrophotography. A steel belt cooler was used as a cooling method, in which the temperature of the cooling water was 10 ° C The product was quenched and kneaded with a thermal conductivity of 0.08 kcal / mhrs under the conditions of 20 liters of cooling water (*) per 1 kg of resin. The various conditions for preparing the resin and the values of its physical properties are listed in Table 1. Then, 6 parts of carbon black, REGAL (trade name) 330R (manufactured by CABOT), 2.5 parts of polypropylene paraffin, NP105 (manufactured by Mitsui Chemicals), and 1 part of Bontron S34 (manufactured by Orient Chemical Industry) limited Charge regulator added to the resin, mixed in a Henschel mixer, and mixed in a twin-shaft kneader (PCM-30 type, Ikekai, Kikai Co., Ltd.) 22 1227384 ^ mouth where the discharge of the twin-shaft kneader The temperature of the resin at the mouth is 150 ° C, and the time between the τ side and the inch is 30 seconds. The kneaded product is then cooled, ground, divided, and prepared to a toner for electrophotography with a size of about 7 microns. Cold fly method It is the same as the above-mentioned quenching method. As described above, * indicates parts by mass, 3 parts of the electrophotographic toner and 97 parts of the carrier are mixed to prepare a developer. The commercially available Nansu photocopier was replaced, and the developer was evaluated based on the quality of the image copied by the photocopier. The results are shown in Table i. Example 2 The same procedure as in Example 1 was performed except that the resin temperature at the discharge port of the biaxial kneader was 185 ° C. The various conditions for preparing the resin and the values of its physical properties are shown in Table 1. Example 3 The same procedure as in Example 2 was performed except that the vinyl resin prepared in Preparation Example was 7 parts and the vinyl resin prepared in Preparation Example B_1 was% parts. The various conditions for preparing the resin and the values of its physical properties are shown in Table 1. Example 4 φ was performed in the same manner as in Example 1 except that the resin temperature at the discharge port of the biaxial kneader was 2000c and the residence time was 30 seconds. The various conditions for preparing the resin and the values of its physical properties are listed in Table Watch. Example 5 The procedure was the same as that of Example 2 except that the vinyl resin prepared in Preparation Example A-1 was changed to the vinyl resin prepared in Preparation Example A-2. The various conditions for preparing the resin and the values of its physical properties are shown in Table 1. 'Examples 6 and 7 except that the vinyl resin prepared in Preparation Example B-1 was changed to the vinyl prepared in Preparation YJ B 2 (corresponding to Example 6) and B-3 (corresponding to Example 7) Except for the resin, the other procedures were carried out in the same manner as in Example 2. The various conditions for preparing the resin and the values of its physical properties are shown in Table 1. > _ Example 8 The same method as in Example 1 was used except that the mixing ratio of the vinyl resin prepared in Preparation Example A-2 and the vinyl resin prepared in Preparation Example B-1 was 97/3. get on. The various conditions for preparing the resin and the values of its physical properties are shown in Table 1. Example 9 Except that the mixing ratio of the vinyl resin prepared in Preparation Example A-1 and the vinyl resin prepared in Preparation Example B-1 was changed from 97/3 to 94/6 Lu, the others were in accordance with the Examples The same method of 2 is performed. The various conditions for preparing the resin and the values of its physical properties are shown in Table i. Example 10 __ 93 parts of the vinyl resin prepared in Preparation Example B-4 and 7 parts of the vinyl resin prepared in Preparation · Example A-3 were mixed in a Henschel mixer, and the resin was biaxially kneaded Machine (Kexn S40, manufactured by Kunmoto Co., Ltd.) to knead the mixed resin in order to carry out the reverse 24 1227384 application, where the resin temperature at the discharge port of the biaxial kneader was 185. ○, the dwell time was 90 seconds, and then the obtained resin was cooled and ground with a grinder (power mill p_3 type, manufactured by Sanei Factor Corporation) to prepare a hueing adhesive for electrophotography. The cooling method is the same as the quenching method in Example 1. Then, 6 parts of carbon black, REGAL (trade name) 330R (manufactured by CABOT Corporation), 2.5 parts of polypropylene paraffin, ΝριΟ5 (produced by Mitsui Chemicals Co., Ltd.), and 1 part of Bontron S34 (produced by Orient Chemical Industry Co., Ltd.) The charge regulator of the company is added to the resin, mixed in a Henschel mixer, and kneaded in a biaxial kneader (PCM_30, manufactured by Ikegai, Kikai · Co., Ltd.), where the discharge port of the biaxial kneader is The resin degree was 155 C, and the residence time was 60 seconds. The kneaded product was then cooled, ground, and classified to prepare a toner for electrophotography having a size of about 7 m. The cooling method is the same as the quenching method in the above-mentioned Example i. 3 parts of an electrophotographic toner and 97 parts of a carrier were mixed to prepare a developer. The commercially available high-speed photocopier was replaced, and the results of measuring the viscosity-elasticity of the toner for electrophotography prepared by the developer 'test based on the image quality copied by the photocopier are shown in Fig. 4. The various conditions for preparing the resin and the values of its physical properties are shown in Table 1. Comparative Example 1 A kneading reaction was carried out in the same manner as in Example 1 except that the resin temperature of the discharge σ of the biaxial kneader was set to 2 and the residence time was 90 seconds, to prepare a toner binder. A toner was prepared and evaluated in the same manner as in Example 1 except that the toner binder prepared in this example was used. The various conditions for testing the resin and the values of its physical properties are shown in Table 2. Comparative Example 2 The same procedure as in Comparative Example 1 was performed except that the resin temperature at the discharge port of the biaxial kneader was 22 ° C. Various conditions for preparing the resin and the values of their physical properties are shown in Table 2. Comparative Example 3 The same procedure as in Comparative Example 1 was carried out except that the vinyl resin prepared in Preparation Example A-1 was 7 parts and the vinyl resin prepared in Preparation Example B-1 was 93 parts. The various conditions for preparing the resin and the values of their physical properties are shown in Table 2. Comparative Example 4 was carried out in the same manner as Comparative Example 1 except that the residence time was 180 seconds. Various conditions for preparing the resin and the values of their physical properties are shown in Table 2. Comparative Example 5 A procedure was carried out in the same manner as in Comparative Example H1, except that the vinyl resin prepared in Preparation Example A-1 was changed to the acetamyl resin prepared in Preparation Example A-2. The various conditions for preparing the resin and the values of their physical properties are shown in Table 2. Comparative Examples 6, 7 Except that the vinyl resin prepared in Preparation Example B-1 was changed to those prepared in Preparation Examples B-2 (corresponding to Comparative Example 6) and B-3 (corresponding to Comparative Example 7) The rest of the vinyl resin was carried out in the same manner as in Comparative Example 1. The various conditions for preparing the resin and their physical properties are shown in Table 2. Comparative Example 8 The same method as Comparative Example 1 was used except that the mixing ratio of the vinyl resin prepared in Preparation Example A-2 and the ethylene resin prepared in Preparation Example B-1 was 97/3. get on. The various conditions for preparing the resin and the values of their physical properties are shown in Table 2. Comparative Example 9 Except that the mixing ratio of the vinyl resin prepared in Preparation Example A-1 and the vinyl resin prepared in Preparation Example B-1 was changed from 97/3 to 94/6, the others were in accordance with the Comparative Example. The same method is performed. Various conditions for preparing the resin and the values of their physical properties are shown in Table 2. Comparative Example 10 A kneading reaction was carried out in the same manner as in Example 10 except that the resin temperature at the discharge port of the biaxial kneader was 220 C and the residence time was 180 seconds, to prepare a toner binder. A toner was prepared in the same manner as in Example 10 except that the toner binder prepared in this example was used. The test results of the viscosity and elasticity of the prepared hueing adhesive are shown in Fig. 4. The various conditions for preparing the resin and the values of their physical properties are shown in Table 2. Evaluation method of toner 1) Fixing performance
複印速率爲72張/分鐘，定影輥溫度改變的間隔爲5 分鐘。砂消除器（塑膠砂消除器“m〇N〇”由T〇mb〇PencU 有限公司製造）在濃黑部分和白背景之間的區域來回轉 27 4 1227384 在力下複印10次。用墨水濃度計測量濃黑部分的 黑度，用濃度比表示調色劑的殘餘比率，在最低温度時， 剩餘的調色劑爲60%或更多（溫度以定影溫度表示） 2)抗偏移性 、田當複印時，指示出發生偏移時的溫度，（溫度以偏移 溫度表示） 3 )結塊性 在5代和5G%相對濕度的環境條件下，調色劑放置！ 週後，用肉眼觀察粉末的聚集度，許價標準如下； ◎:粉末沒有聚集， 器時，聚集物 〇,粉末輕微聚集，但當輕微搖 鬆散， 器’聚集物也沒 △，有些聚集，即使長時間地搖動容 有鬆散。 σ X’粉末完全聚集。 4)可磨性 虽製備調色劑時，取出已在雙 的卹八$ ι 2 ^ 匕口機中捏合並冷卻 π刀産物並研磨’研騎末的 目，妙你—J J 具粒從爲10-16 …、、後在射&研磨機中進一步研磨。 ^ 抑、 量粒徑分佈，0得抑/-一 ，、“、、油計數器測 刀师獲侍粒毪爲5-20//的比率。 ◎ ; 85%或更高 28 1227384 〇；70-85% Δ ； 50-70% X ； <50% 5)持續顯影性 用市售的高速影印機（複印速率爲72張/分）連續複 印10000張後，複印模板，以檢測再生産能力。基紙的行 寬爲100 // m，用顯微鏡觀察5個點的行寬，然後再複印， 定影後，測試複印紙的5個點行寬。分別獲得基紙和複印籲 紙的行寬的平均值，按如下標準評價，其中根據基紙的行 寬和複印紙的行寬之間的差別來評價。行寬的增加值 複印紙的行寬-基紙的行寬。 〇 ; δ <5 β m A ； 5<δ <1〇^ m X ; 5 >10 # mThe copy rate was 72 sheets / minute, and the interval between the fixing roller temperature changes was 5 minutes. The sand eliminator (plastic sand eliminator "m〇N〇" manufactured by Tombo PencU Co., Ltd.) rotates in the area between the thick black part and the white background. 27 4 1227384 Makes 10 copies under force. Measure the blackness of the thick black portion with an ink densitometer, and use the density ratio to indicate the residual ratio of the toner. At the lowest temperature, the remaining toner is 60% or more (temperature is expressed at the fixing temperature). 2) Anti-offset Migration and field when copying, indicates the temperature at which the shift occurs, (temperature is expressed as the shift temperature) 3) Lumpiness Under the environmental conditions of 5th generation and 5G% relative humidity, the toner is placed! After one week, the degree of aggregation of the powder was observed with the naked eye, and the allowable price standard was as follows: ◎: The powder did not aggregate, the aggregate was 0, and the powder was slightly aggregated, but when it was loosened slightly, the aggregate was not △, and some aggregated. Even if shaken for a long time, there is looseness. The σ X 'powder is completely aggregated. 4) Although the grindability, when preparing the toner, take out the product which has been kneaded in a double shirt, and then knead and cool the product of the π knife and grind the 'Kanji's eyes, Miaoyou—JJ 粒粒 从 为10-16…, and then further polished in a shot & grinder. ^ Yield and particle size distribution, 0 is Yil /-Yi, ",", oil counter stylist gets a grain size of 5-20 //. ◎; 85% or higher 28 1227384 〇; 70- 85% Δ; 50-70% X; < 50% 5) Continuous development using a commercially available high-speed photocopier (copying rate of 72 sheets / minute) to continuously copy 10,000 sheets, and then copy the template to test the reproduction capacity. The line width of the base paper is 100 // m. Observe the line width of 5 dots with a microscope, and then make a copy. After fixing, test the line width of 5 dots on the copy paper. Obtain the line width of the base paper and copy paper. The average value is evaluated according to the following criteria, where the evaluation is based on the difference between the line width of the base paper and the line width of the copy paper. The increased value of the line width is the line width of the copy paper-the line width of the base paper. 〇; δ < 5 β m A; 5 < δ < 1〇 ^ m X; 5 > 10 # m
29 122738429 1227384
τ< 實施例10 La3」 L M J 1 93/7 | 50000 0.039 ON 00 m 00 rH rH <CN 00 00 cn § 3420 5000 1580 172 156 (N (N ◎ ON 00 〇 實施例9 |A±J B-l | 94/6 I 30000 0.039 CO 00 vn 00 r—t (N τ-Η 〇 ο (Ν 4430 6000 1570 170 CO r-H 240 〇 (Ν 00 〇 實施例8 A-2 B-l 93/7 70000 t-H d CO K 00 in 170 (N rH o CO ο cn cn § 3900 5600 1700 1 167 1 CO Ό rH in cn (N ◎ Ό 00 〇 實施例7 < B-3 97/3 30000 0.039 cn T-H in vn 00 rH (N rH 00 00 容 3750 | 4800 1050 vn rH Li6〇 1 215 1 < 〇 實施例6 LalJ B-2 | 97/3 | 30000 0.039 2i：5 1 S in 00 rH (N o cn ο |3300 4400 1100 t-H t-H 1 21〇 1 ◎ (Ν 〇 實施例5 ,.A-2j B-l | 97/3 | 70000 d cn 00 vn vn 00 t-H <N ^rH cn cn ο 3980 1 5560 1 1 1580 1 o rH o rH v〇 CO <N 〇 00 〇 實施例4 A-l Bi」 97/3 30000 0.039 cn 00 「200 rH Ό m § 3300 4800 1500 CO rH 艺 r-H 220 ◎ τΗ σ\ 〇 實施例3 1 A-1 」 1 B·1 1 Γ 93/7 1 30000 0.039 m 00 in vn 00 t-H (N rH CO m 4600 6200 1600 00 r—1 in 240 ◎ § 〇 實施例2 1 A-l 1 B-l | 97/3 | 30000 | 0.039 | cn 00 in in 00 rH § (N νο v〇 cn 3300 1 4800 j 1500 172 寸 vn 220 ◎ Ον 〇 實施例1 A-l B-l 97/3 30000 0.039 cn 00 1 (N 00 寸 CN (N 3050 4750 1700 \o t-H 泛 t-H 220 〇 〇 樹脂A 樹脂B 重量比（B/A) 樹脂A Mw 樹脂A環氧值（Eq/lOOg) 樹脂B酸值（mgKOH/g) 樹脂 B Tg(°C) 在雙軸捏合機中的樹脂溫度 在雙軸捏合機中的停留時間 分子量峰值 （xlOOO) 完全反應凝膠 （％) -X 凝膠 —Υ o o * g 簽 Tg (°〇 σ 0 (Pa) G，200 (Pa) △G， （Pa) 在G’ 0溫度（°C) 定影溫度（°C) 偏移溫度（°C) 結塊性能 财磨性 持續顯影性能 1227384 比較 實施例10 A-3 B-4 93/7 i 50000 0.039 〇\ οό 220 180 <〇· rH 3 Ο § 4970 5000 L.J.84 00 rH 220 ◎ 〇 〇 比較 實施例9 A-1 gl1 94/6 30000 0.039 m 00 vn 200 § (N rH o 00 cn U1 σ\ s 5950 6000 VT) 00 τ-Η 客 τ-Η 240 〇 〇 比較 實施例8 A-2 B-1 93/7 70000 τ-Η d m 00 IT) 200 (N 00 (N cn σ\ s 5540 5600 00 τ-Η CO ON rH 230 ◎ 〇 比較 實施例7 A-1 B-3 97/3 30000 0.039 m 200 (N 00 芸 SR 4750 4800 tr> 00 ^-Η 182 215 <1 s 比較 實施例6 A-1 B-2 97/3 30000 0.039 —2·5」 s 200 (N rH o vn o\ ο\ 4350 4400 00 τ-Η rH 1 210 ί ◎ <1 比較 實施例5 A-2 B-1 97/3 70000 d <T) 00 tn 200 (N r-H cn cn rH cn s 5500 5560 S § rH 192 230 〇 00 < 比較 實施例4 A-1 B-1 97/3 30000 0.039 cn l> 00 in 200 180 (N rH r-j s 4730 4800 ο 179 00 τ-Η ◎ S5 <1 比較 實施例3 A-1 B-1 93/7 30000 「0.039 cn ϊ> 00 200 (N rH cn a\ 6100 6200 ο τ-Η 卜 200 240 ◎ 〇 比較 實施例2 A-1 B-1 97/3 30000 0.039 cn l> 00 tn 220 (N rH r-| r-| ο τΗ s 4850 4800 Ο I I 1 187 (Ν ◎ 00 < 比較 實施例1 A-1 B-1 97/3 30000 0.039 cn 00 200 CN 00 r-j 艺 σ\ V〇 「4770 4750 1 1 1 1 180 to 〇 〇 >< /^Ν 〇 r-H g Ο ω Kf\ 1$: o 沴 * OJJ B >< Ρ P -δ- r^\ Μ Μ 驗 /^N 〇3 /~Ν o。 〇。 w 德 Φ £ 賴 郏 Ph ο < PQ Jj < < PQ PQ _ o。 o 朗 蘧 _ 伽 驗 赛 〇 Cn Ο Ο 率 Φ ϋ 〇 < Ητ < Example 10 La3 ″ LMJ 1 93/7 | 50000 0.039 ON 00 m 00 rH rH < CN 00 00 cn § 3420 5000 1580 172 156 (N (N ◎ ON 00 〇 Example 9 | A ± J Bl | 94/6 I 30000 0.039 CO 00 vn 00 r-t (N τ-Η 〇ο (Ν 4430 6000 1570 170 CO rH 240 〇 (Ν 00 〇 Example 8 A-2 Bl 93/7 70 000 tH d CO K 00 in 170 (N rH o CO ο cn cn § 3900 5600 1700 1 167 1 CO Ό rH in cn (N ◎ Ό 00 〇 Example 7 < B-3 97/3 30000 0.039 cn TH in vn 00 rH (N rH 00 00 capacity 3750 | 4800 1050 vn rH Li6〇1 215 1 < 〇 Example 6 LalJ B-2 | 97/3 | 30000 0.039 2i: 5 1 S in 00 rH (N o cn ο | 3300 4400 1100 tH tH 1 21〇1 ◎ (N 〇 Example 5 ..A-2j Bl | 97/3 | 70000 d cn 00 vn vn 00 tH < N ^ rH cn cn ο 3980 1 5560 1 1 1580 1 o rH o rH v 〇CO < N 〇00 〇 Example 4 Al Bi "97/3 30000 0.039 cn 00" 200 rH Ό m § 3300 4800 1500 CO rH yi rH 220 ◎ τΗ σ \ 〇 Example 3 1 A-1 '' 1 B 1 1 Γ 93/7 1 30000 0.039 m 00 in vn 00 tH (N rH CO m 4600 6200 1600 00 r—1 in 240 ◎ § 〇 Example 2 1 Al 1 Bl | 97/3 | 30000 | 0.039 | cn 00 in in 00 rH § (N νο v〇cn 3300 1 4800 j 1500 172 inch vn 220 ◎ Ον 〇 Example 1 Al Bl 97/3 30000 0.039 cn 00 1 (N 00 inch CN (N 3050 4750 1700 \ o tH pan tH 220 〇〇 Resin A Resin B weight ratio (B / A) Resin A Mw Resin A epoxy value (Eq / lOOg ) Resin B acid value (mgKOH / g) Resin B Tg (° C) Resin temperature in a biaxial kneader Residual time in a biaxial kneader Molecular weight peak (xlOO) Complete reaction gel (%) -X Coagulation Glue—Υ oo * g signed Tg (° 〇σ 0 (Pa) G, 200 (Pa) △ G, (Pa) at G '0 temperature (° C) fixing temperature (° C) offset temperature (° C) Agglomeration performance Financial development Continued development performance 1227384 Comparative Example 10 A-3 B-4 93/7 i 50000 0.039 〇 \ οό 220 180 < 〇 · rH 3 〇 § 4970 5000 LJ84 00 rH 220 ◎ 〇〇Comparative Example 9 A-1 gl1 94/6 30000 0.039 m 00 vn 200 § (N rH o 00 cn U1 σ \ s 5950 6000 VT) 00 τ-Η Guest τ-Η 240 〇〇 Comparative Example 8 A-2 B -1 93/7 70000 τ-Η dm 00 I T) 200 (N 00 (N cn σ \ s 5540 5600 00 τ-Η CO ON rH 230 ◎ ○ Comparative Example 7 A-1 B-3 97/3 30000 0.039 m 200 (N 00 Yun SR 4750 4800 tr > 00 ^ -Η 182 215 < 1 s Comparative Example 6 A-1 B-2 97/3 30000 0.039 -2 · 5 ″ s 200 (N rH o vn o \ ο \ 4350 4400 00 τ-Η rH 1 210 ί ◎ < 1 Comparative Example 5 A-2 B-1 97/3 70000 d < T) 00 tn 200 (N rH cn cn rH cn s 5500 5560 S § rH 192 230 〇00 < Comparative Example 4 A-1 B-1 97/3 30000 0.039 en l > 00 in 200 180 (N rH rj s 4730 4800 ο 179 00 τ-Η ◎ S5 < 1 Comparative Example 3 A-1 B-1 93/7 30000 `` 0.039 cn ϊ > 00 200 (N rH cn a \ 6100 6200 ο τ-Η 200 200 240 ◎ 〇 Comparative Example 2 A-1 B-1 97/3 30000 0.039 cn l > 00 tn 220 (N rH r- | r- | ο τΗ s 4850 4800 〇 II 1 187 (N ◎ 00 < Comparative Example 1 A-1 B-1 97/3 30000 0.039 cn 00 200 CN 00 rj σσ σ \ V〇 「4770 4750 1 1 1 1 180 to 〇〇 > < / ^ Ν 〇rH g Ο ω Kf \ 1 $: o 沴 * OJJ B > < P P -δ- r ^ \ Μ assay / ^ N 〇3 / ~ Ν o. 〇. w Germany Φ £ Lai 郏 Ph ο < PQ Jj < < PQ PQ _ o. o Lang 蘧 _ Gamma Test 〇 Cn 〇 〇 Rate Φ ϋ 〇 < Η
1227384 實施例的測試結果列於表1中’比較實施例的測試結 果列於表2中。實施例和比較實施例中的凝膠含量和定影 溫度之間的關係列於圖1中。實施例和比較實施例中的完 全反應的凝膠含量和偏移溫度之間的關係列於圖2中。實 施例和比較實施例中的定影温度和偏移溫度之間的關係 列於圖3中。The test results of the 1227384 example are listed in Table 1 and the test results of the comparative example are listed in Table 2. The relationship between the gel content and the fixing temperature in the examples and comparative examples is shown in FIG. The relationship between the gel content and the offset temperature of the complete reaction in the examples and comparative examples is shown in FIG. 2. The relationship between the fixing temperature and the offset temperature in the examples and comparative examples is shown in FIG.
本發明人經過仔細地研究，發現凝膠含量和定影溫度 有密切的關係，如圖1所示，還發現完全反應的凝膠含量 和偏移溫度有密切的關係，如圖2所示。另外，如上所述， 本明人發現在雙轴捏合過程中，通過控制交聯反應可以控 制凝膠含量，結果，他們發明了一種獲得所需定影性的方 法。另一方面，用本發明人（曰本專利特許公開〇9_3i9i4〇) 開發的技術可以控亲J完全反應的凝膠含量，利關2所示 的關係，可以獲得所需的偏移性。After careful research, the present inventors found that there is a close relationship between the gel content and the fixing temperature, as shown in Fig. 1, and also a close relationship between the fully reacted gel content and the offset temperature, as shown in Fig. 2. In addition, as described above, the present inventors discovered that the gel content can be controlled by controlling the crosslinking reaction during the biaxial kneading process, and as a result, they invented a method for obtaining desired fixability. On the other hand, the technology developed by the present inventor (Japanese Patent Laid-open Publication No. 09_3i9i4〇) can control the gel content of the complete reaction of the pro-J, and the relationship shown in Fig. 2 can obtain the required offset.
如上所述’本發明人已研究出—種通過㈣凝膠含 和完全反應的凝膠含量來製備低溫時定影性和偏移性 異的調色黏合劑的方法。如圖3所示，實施例與比較實 例相比，當定影溫度相同時，可以製備偏移溫度高的調 2劑，當偏移溫度相同時，可以製備定影溫度低的調 黏合劑。 本發明的調色黏合劑用 有優異的性能，如低溫時定 發明的調色黏合劑具有優異 性和持續顯影性均優良，如 於向速節能的影印機中時，具 衫性和抗偏移性好。而且，本 的實用性，如抗結塊性、耐磨 表1所示。 32 !227384 【圖式簡單說明】 圖1是表示實施例和比較實施例中的凝膠含量和定影溫 度之間的關係的圖， 圖2是表示實施例和比較實施例中的完全反應的凝膠含 量和偏移溫度之間的關係的圖； 圖3是表示實施例和比較實施例中的定影溫度和偏移溫 度之間的關係的圖； 圖4是表示實施例10和比較實施例10中的調色黏合劑 的貯存模量G > s和溫度之間的關係的圖。 _ 【元件代表符號簡單說明】 無As described above, the present inventors have developed a method of preparing a toning adhesive having different fixability and offset properties at low temperatures by using a gel content and a fully-reacted gel content. As shown in Fig. 3, when the fixing temperature is the same in the embodiment and the comparative example, a modifier with a high offset temperature can be prepared, and when the offset temperature is the same, a binder with a low fixing temperature can be prepared. The toning adhesive of the present invention has excellent properties. For example, the toning adhesive of the invention at a low temperature has excellent performance and continuous development. When used in a fast-speed energy-saving photocopier, it has shirting and anti-offset properties. Good mobility. In addition, the practicality of this product is shown in Table 1 in terms of anti-caking resistance and abrasion resistance. 32! 227384 [Schematic description] Fig. 1 is a graph showing the relationship between the gel content and the fixing temperature in Examples and Comparative Examples, and Fig. 2 is a graph showing the fully reacted gels in Examples and Comparative Examples. A graph showing the relationship between the glue content and the offset temperature; FIG. 3 is a graph showing the relationship between the fixing temperature and the offset temperature in the embodiment and the comparative embodiment; FIG. 4 is a view showing Example 10 and the comparative example 10 A graph of the relationship between the storage modulus G > s and the temperature of the hueing adhesive in. _ [Simple description of component representative symbols] None
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